Heterolytic Cleavage of H<sub>2</sub> at a Sulfur‐Bridged Dinuclear Ruthenium Center

Sellmann, Dieter; Prakash, Raju; Heinemann, Frank W.; Moll, Matthias; Klimowicz, Maria

doi:10.1002/anie.200453717

Cited by 59 publications

(33 citation statements)

References 34 publications

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“…Many of these complexes contain thiolate (examples include 37 and 38 ) and/or thioether donor group(s) which bind the {Ru-NO} 6 core quite tightly [170,171]. The thiolato sulfur donors in the five-coordinate nitrosyl 37 are reactive and readily undergo subsequent reactions to afford complexes with extended S 4 N coordination such as [Ru(NO)(pyS 4 )](Tos) (Tos = tosylate, 39, 40 ) [172–174]. …”

Section: Uv Photoactivitymentioning

confidence: 99%

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Photoactive ruthenium nitrosyls: Effects of light and potential application as NO donors

Rose

Mascharak

2008

Coordination Chemistry Reviews

308

282

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Section: Uv Photoactivitymentioning

confidence: 99%

“…In 2004, Sellmann and co-workers reported the photoactivity of nitrosyls of the type [Ru(NO)(py t Bu S 4 )] + [174]. Upon exposure to UV light, [Ru(NO)(py t Bu S 4 )]Br ( 40 ) releases NO and is converted into the corresponding Ru(III) species [Ru(Br)(py t Bu S 4 )] (Fig.…”

Section: Uv Photoactivitymentioning

confidence: 99%

Photoactive ruthenium nitrosyls: Effects of light and potential application as NO donors

Rose

Mascharak

2008

Coordination Chemistry Reviews

308

282

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“…Systems that heterolytically cleave H 2 intramolecularly (Section 1.2) commonly catalyze D 2 /H 2 O exchange, often via an unobserved or transient D 2 complex. This is well exemplified by Sellmann's Ni, Fe, and Ru complexes containing multidentate sulfur ligands that cleave D 2 to give D-M)SD species that undergo proton exchange with water [94]. These and related systems model dihydrogen cleavage and isotopic exchange reactions observed in biological enzymes such as hydrogenases and nitrogenases [9].…”

Section: Catalysis Of Isotopic Exchange By H 2 Complexesmentioning

confidence: 99%

Catalytic Processes Involving Dihydrogen Complexes and Other Sigma-bond Complexes

Kubas

2005

Catal Lett

109

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“…1), which has attracted inorganic and organometallic chemists attempting to model both the structure and physicochemical properties. Thiolate-bridged Ni-Fe complexes have been synthesized as structural models of the active site (16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26), and sulfurligated mono-and dinuclear transition metal complexes have been reported to promote H 2 activation mimicking the function of [NiFe] hydrogenase (27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38)(39)(40)(41). However, synthesis of better structural/functional models remains challenging.…”

mentioning

confidence: 99%

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) ₃ Fe( μ -S ^t Bu) ₃ Ni{SC ₆ H ₃ -2,6-(mesityl) ₂ } and reversible CO addition at the Ni site

Ohki

Yasumura

Ando

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

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A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, ðCOÞ 3 Feðμ-S t BuÞ 3 NiðSDmpÞ, 1 (Dmp¼ C 6 H 3 -2;6-ðmesitylÞ 2 ), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex ½ðCOÞ 3 Feðμ-S t BuÞ 3 Ni 2 ðμ-BrÞ 2 , 2 with NaSDmp at −40°C. The nickel site of complex 1 was found to add CO or CN t Bu at −40°C to give ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCOÞ ðSDmpÞ, 3, or ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCN t BuÞðSDmpÞ, 4, respectively. One of the CO bands of 3, appearing at 2055cm −1 in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CN t Bu adduct 4 is more robust.iron | nickel | thiolates B iological hydrogen evolution and uptake are mediated by hydrogenase enzymes (1-7). The most prevalent family are the [NiFe] hydrogenases, and various forms have been identified (8)(9)(10)(11)(12)(13)(14)(15). A unique feature of the [NiFe] hydrogenase is the common organometallic dinuclear Ni-Fe frame at the active site ( Fig. 1), which has attracted inorganic and organometallic chemists attempting to model both the structure and physicochemical properties. Thiolate-bridged Ni-Fe complexes have been synthesized as structural models of the active site (16-26), and sulfurligated mono-and dinuclear transition metal complexes have been reported to promote H 2 activation mimicking the function of [NiFe] hydrogenase (27-41). However, synthesis of better structural/functional models remains challenging.One interesting aspect of the [NiFe] hydrogenase is the reversible inhibition of the active site by CO. According to a crystallographic analysis of the CO-inhibited form of the [NiFe] hydrogenase obtained from Desulfovibrio vulgaris Miyazaki F (D. v. Miyazaki F), a CO molecule is coordinated at the nickel center (42). It has been suggested that this nickel-bound CO can be liberated and the catalytic activity recovered, upon flushing with a stream of N 2 (43), or by white-light irradiation at 20 K (44). Herein we report the synthesis of a thiolate-bridged dinuclear Ni-Fe complex ðCOÞ 3 Feðμ-S t BuÞ 3 NiðSDmpÞ, 1, carrying a bulky thiolate SDmp (Dmp¼C 6 H 3 -2;6-ðmesitylÞ 2 ) at Ni, and its CO and CN t Bu adducts, ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCOÞðSDmpÞ, 3, and ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCN t BuÞðSDmpÞ, 4. The reaction of 1 with CO occurs reversibly to give 3, while the analogous CN t Bu adduct 4 is robust. We also report the x-ray crystal structures of 1, 3, and 4. Results and DiscussionSynthesis and Structure of ðCOÞ 3 Feðμ-S t BuÞ 3 NiðSDmpÞ, 1. We have reported that a linear tetranuclear Fe-Ni-Ni-Fe complex ½ðCOÞ 3 Feðμ-S t BuÞ 3 Ni 2 ðμ-BrÞ 2 , 2, which was synthesized from FeBr 2 ðCOÞ 4 þNaðS t BuÞþNiBr 2 ðEtOHÞ 4 (1∶2∼3∶1), serves as a convenient precursor for the synthesis of thiolate-bridged dinuclear Ni-Fe complexes (17). The penta-coo...

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Heterolytic Cleavage of H₂ at a Sulfur‐Bridged Dinuclear Ruthenium Center

Cited by 59 publications

References 34 publications

Photoactive ruthenium nitrosyls: Effects of light and potential application as NO donors

Photoactive ruthenium nitrosyls: Effects of light and potential application as NO donors

Catalytic Processes Involving Dihydrogen Complexes and Other Sigma-bond Complexes

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) ₃ Fe( μ -S ^t Bu) ₃ Ni{SC ₆ H ₃ -2,6-(mesityl) ₂ } and reversible CO addition at the Ni site

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Heterolytic Cleavage of H2 at a Sulfur‐Bridged Dinuclear Ruthenium Center

Cited by 59 publications

References 34 publications

Photoactive ruthenium nitrosyls: Effects of light and potential application as NO donors

Photoactive ruthenium nitrosyls: Effects of light and potential application as NO donors

Catalytic Processes Involving Dihydrogen Complexes and Other Sigma-bond Complexes

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) 3 Fe( μ -S t Bu) 3 Ni{SC 6 H 3 -2,6-(mesityl) 2 } and reversible CO addition at the Ni site

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Heterolytic Cleavage of H₂ at a Sulfur‐Bridged Dinuclear Ruthenium Center

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) ₃ Fe( μ -S ^t Bu) ₃ Ni{SC ₆ H ₃ -2,6-(mesityl) ₂ } and reversible CO addition at the Ni site